Spiro compounds

ABSTRACT

Compounds which contain a group bonded directly to an aromatic nucleus of the formula 
     
         --(CH.sub.2 --).sub.n --X                                  1. 
    
     in which n is a positive integer having a value of at least 2 and X represents a removable substituent.

This is a division of application Ser. No. 195,031, filed on Nov. 2,1971, now U.S. Pat. No. 3,873,615.

The invention relates to spiro compounds with dyestuff character, and tocompounds which are suitable for the manufacture of such spiro compoundsand which contain an aliphatic group, directly bonded to an aromaticnucleus, which possesses a removable substituent, especially a group ofthe formula

    --(CH.sub.2).sub.n --X                                     1.

wherein n denotes a positive integer having a value of at least 2 and Xdenotes a removable substituent.

Amongst the starting compounds which are suitable for the manufacture ofspiro compounds according to the invention, particular interest attachesto those which contain a group of the formula (1), which is directlybonded to an aromatic nucleus of an at least bicyclic aromaticsix-membered ring system, and wherein n denotes a positive integerhaving a value of at least 2 and X denotes a halogen atom, an acyloxy orsulphato, thiosulphato or tosylate group or a quaternary ammonium group.These starting compounds can themselves possess dyestuff character, orthey can be converted into compounds with dyestuff character, forexample by coupling, acylation or the like. The number n is preferablyless than 10, for example 4 or 5.

Important compounds of the type described above are above all thosewhich contain a grouping of the formula (1), wherein n = 2.

As an example, there may especially be mentioned compounds whichcorrespond to the formula ##SPC1##

Wherein X represents a chlorine or bromine atom, or compounds whichcontain a radical of the formula (2), which is bonded to anotherradical, for example via an azo, amino, carbonyl, oxycarbonyl,aminocarbonyl, sulphonyl or sulphamino bridge or the like.

In this case either the other radical to which the radical of theformula (2) is bonded is a chromogen, or only both radicals togetherform a dyestuff, such as, for example, in the azo series. The ringsystem of the formula (2) can contain further substituents, such as, forexample, halogen atoms, amino, nitro, sulphonic acid, carboxyl,sulphonyl, sulphonamino, alkyl, aryl, alkoxy, aryloxy, acyl andacylamino groups and the like. Preferably, however, the compounds of theformula (2) or the radical of the formula (2) are unsubstituted.

The corresponding spiro compounds can be manufactured from thenaphthalene derivatives of the formula (2) by treatment with sodiumhydroxide solution, for example in ether or acetone, in which case,hydrogen halide is split off and cyclisation to give the spirodienone ofthe formula ##SPC2##

Occurs, or a compound is formed which contains a radical of the formula(3). As regards bonding to another radical, or possible furthersubstituents, the same applies here as has been said in the elucidationof the formula (2).

Compounds of the formula (2), for example of1-hydroxy-4-(β-iodoethyl)-naphthalene, can be manufactured by reactingα-naphthol with ethylene oxide in the presence of aluminium chloride andsubsequently reacting the resulting1-(β-hydroxyethoxy)-4-(β-hydroxyethyl)-naphthalene with hydrogen iodide.In another method of manufacture, α-naphthol again serves as thestarting substance. It is nitrated with nitric acid to give4-nitro-naphthol-(1), which is then reduced by means ofhydrogen/platinum catalyst to give 4-amino-naphthol-(1). The resultingproduct is converted into the corresponding zinc chloride adduct bymeans of metallic zinc and hydrochloric acid in tetrahydrofurane, andthe 1,4-diazoxide is finally obtained from the adduct by diazotisationwith sodium nitrite and hydrochloric acid. The 1,4-diazoxide is nowconverted by photolysis in the presence of an olefine into thecorresponding spirodienone, the irradiation being carried out throughpotassium chromate/dichromate solution as a filter, so as to absorbradiation of undesired wavelengths and thus prevent direct activation ofthe photolabile spirodienone produced. The progress of the reaction canbe seen from the evolution of nitrogen or the disappearance of theorange diazoxide colour. Ethylene may especially be mentioned as anolefine which can be used in this process. The spirodienone obtained canbe freed of the excess olefine by concentration and be purified byrecrystallisation from cold pentane. Reaction of the spirodienoneobtained [of the type of the formula (3)] with a hydrogen halide acid,for example hydrogen bromide or hydrogen iodide, opens the ring producedby condensation with the olefine, and the desired1-hydroxy-4-(ω-halogenalkyl)-naphthalene is produced. Both the methodsdescribed furnish the end product in good yields. A further, new methodis described in the embodiment of the Example 1.

The linkage of compounds of the formulae (2) or (3) to other radicalswhich either by themselves already possess dyestuff character ortogether with the radical of the formula (2) or (3) form a compound withdyestuff character can be carried out in various ways.

Thus it is, for example, possible to convert1-methoxy-4-(β-hydroxyethyl)-naphthalene, by nitration with nitric acidat 0°C, into 1-methoxy-2-nitro-4-(β-hydroxyethyl)-naphthalene, and toconvert this, by reaction with hydrogen iodide, into2-nitro-4-(β-iodoethyl)-naphthol-(1), to convert this, by reduction withhydrogen in the presence of Raney nickel in ethanol, into thecorresponding 2-amino compound, and finally to convert the latter, bycondensation with a sulphochloride possessing dyestuff character, into adyestuff of the formula ##SPC3##

Possible radicals F are, for example, those of the anthraquinone,phthalocyanine or azo series, or the like.

According to another method,1-hydroxy-4-(β-chlorosulphatoethyl)-naphthalene-2-sulphochloride can beobtained by reacting, for example,1-hydroxy-4-(β-hydroxyethyl)-naphthalene with chlorosulphonic acid incarbon tetrachloride, and the product can then be reacted with an aminewhich possesses dyestuff character, to form the correspondingnaphthalene-sulphonic acid amide. Here again the chromophoric radical ofthe amine can belong to the most diverse classes of dyestuffs.

A particularly interesting class of the compounds according to theinvention are the azo dyestuffs of the general formula ##SPC4##

wherein R denotes a radical of the benzene or naphthalene series, whichare, for example, obtained from 4-(β-halogenoethyl)naphthol-(1) bycoupling with an appropriate diazotised amine, and subsequent removal ofhydrogen halide. When acting on cellulose fibres, the three-memberedring reacts with the hydroxyl groups of the cellulose to open the ringand form a stable ether bridge to the cellulose molecule.

The spiro compounds according to the invention, possessing dyestuffcharacter, the compounds of the formulae (2) and (3), and the compoundspossessing dyestuff character which contain a radical of the formula (2)or (3), are new. They possess the property of fibre reactivity, that isto say they are capable of forming covalent chemical bonds with thehydroxyl groups of cellulose or the amino groups of polyamides.

They are therefore suitable for dyeing and printing the most diversematerials such, for example, as silk, leather, wool, synthetic fibresfrom polyamides or polyurethanes, and polyhydroxylic materials such, forexample, as cellulose-containing materials of fibrous structure, such aslinen, staple rayon, regenerated cellulose, cotton and the like.

The most important compounds according to the invention are those whichcontain a water-solubilising group, especially a sulphonic acid group.These dyestuffs are preferably used for dyeing nitrogenous fibres such,for example, as polyamides, polyurethanes, silk, leather, and especiallywool, for example from a weakly acid, neutral or weakly alkaline bath,optionally with the addition of the customary assistants, for exampleethylene oxide condensation products of high molecular amines, and fordyeing cellulose materials, especially cotton, for example by theexhaustion process from a dilute liquor, from an alkaline aqueous bathwhich optionally has a high salt content, and especially by the paddyeing process, in which the goods are impregnated with aqueous dyestuffsolutions which optionally also contain salt, and the dyestuffs arefixed after an alkaline treatment or in the presence of alkali, ifappropriate accompanied by a heat treatment.

The reactive dyestuffs according to the invention are fixed on cotton ina weakly acid to alkaline solution, and on wool and syntheticpolyamides, preferably in an acid medium.

Because of the stability of the fibre-dyestuff bond produced by thereactive radical, the dyeings obtained with the new dyestuffs on thematerials mentioned yield excellent fastness properties, especially wetfastness properties.

To improve the wet fastness properties it is advisable to subject thedyeings and prints obtained to a thorough rinse with cold and hot water,optionally with the addition of an agent which has a dispersing actionand assists the diffusion of the non-fixed material.

The water-soluble reactive dyestuffs according to the invention are alsosuitable for printing, for example on cotton but also for printingnitrogen-containing fibres, for example wool, silk or mixed fabricscontaining wool.

In the examples which follow, the parts, unless otherwise stated, denoteparts by weight and the percentages denote percentages by weight. Therelationship of parts by weight to parts by volume is the same as of thegram to the cubic centimeter.

EXAMPLE 1

322 g of 1-naphthol are rapidly treated with 1.44 liters of 10% strengthpotassium hydroxide solution in a four-necked flask, whilst stirring.280 g of dimethyl sulphate are now added dropwise from a droppingfunnel, whilst cooling with ice water, in such a way that thetemperature remains below 40°C. The dark red reaction mixture isthereafter heated on a boiling water bath for 30 minutes. After cooling,the dark organic phase is separated off, the aqueous phase is extractedwith ether, the two organic phases are combined, washed with 2 Npotassium hydroxide solution and water and dried over calcium chloride,and the solvent is distilled off on a rotary evaporator. The reactionproduct is purified by distillation in a high vacuum.

264.8 g of the 1-methoxy-naphthalene obtained are dissolved in 400 ml ofcarbon tetrachloride and introduced into a 2 liter five-necked flaskwith stirrer, thermometer, gas inlet tube, condenser and droppingfunnel. A solution of 283 g of bromine in 130 ml of carbon tetrachlorideis now slowly added dropwise over the course of 6 hours in such a waythat the temperature does not exceed 0°C (cooling by means of anice/sodium chloride bath). In order to ensure expulsion of the hydrogenbromide produced, a slight stream of dry nitrogen is bubbled through thereaction mixture during the addition of the bromine, and subsequentlyovernight.

The clear yellow solution is then washed with water containingbisulphite (10 g of sodium bisulphite in 600 ml of water) extracted byshaking three times with 300 ml of dilute potassium hydroxide solutionand ice in each case, washed repeatedly with water and freed of thesolvent on a rotary evaporator, and the residue is distilled in a highvacuum.

238.5 g of the 1-bromo-4-methoxy-naphthalene obtained are dissolved in200 ml of diethyl ether and introduced into a 3 liter five-neck flask.31 g of magnesium filings which have been washed with ether, dried for24 hours in a high vacuum and warmed in a closed flask with 200 mg ofiodine over a flame, are then added. A mixture of 38 g of ethylenebromide, 50 ml of diethyl ether, 150 ml of benzene and 10 ml of freshlydistilled methyl iodide is now slowly added dropwise over the course of20 hours from a Hershberg dropping funnel, in the course of which thebath temperature should initially be 55°C, and 75°C after 5 hours and upto the end of the addition.

After completion of the addition, the reaction solution is cooled to 0°C. 53 g of ethylene oxide are now added to 250 ml of diethyl ethercooled to -50°C, and this solution is added dropwise to the Grignardreagent, with vigorous stirring, in such a way that the temperature isabout 0°C (cooling with an ice/sodium chloride bath), whereupon a yellowprecipitate is produced. After completion of the addition the mixture isfurther stirred until room temperature is reached, and is subsequentlyboiled for one hour under reflux.

150 ml of concentrated sulphuric acid in 1 liter of ice/water are thenslowly added while cooling strongly, whereupon the precipitate dissolvescompletely and the temperature rises somewhat despite the cooling. Theyellow organic phase is now separated off, the aqueous phase isextracted with ether, the combined organic phases are washed 3 timeswith 1 liter of 5% strength potassium hydroxide solution at a time,repeatedly washed with water and dried with 200 g of anhydrous sodiumcarbonate. Finally, the solvents are distilled off on a rotaryevaporator, and the oil, which shows a blue-green iridiscence, isdistilled under a high vacuum.

100 g of the β-4-methoxy-1-naphthyl-ethyl-alcohol obtained are dissolvedin 3 liters of glacial acetic acid. 400 ml of concentrated hydriodicacid (57% strength), which has been freshly distilled, are added. Thesolution is heated to the boil (110°C), whereupon a mixture of methyliodide/water/acetic acid is evolved. At the same time, a vigorous streamof nitrogen is passed through the reaction mixture, but care must betaken to periodically replace the acetic acid evolved, so thatexcessively high concentrations of the adduct and product do not buildup. After 2 hours, the reaction is complete. The hot reaction solutionis filtered and treated with 10 g of sodium bisulphite in 2 liters ofwater, whereupon the product precipitates. The product is recrystallisedfrom benzene/carbon tetrachloride or from ethanol/water.

3.24 g of 2-naphthylamine-5,7-disulphonic acid (sodium salt) aredissolved in 5 ccs of concentrated hydrochloric acid and 100 ml ofwater. 10 ml of sodium nitrite solution are added dropwise to thesolution cooled to 0°C.

2.98 g of β-4-hydroxy-1-naphthyl-ethyl iodide are dissolved in 200 ml ofmethanol, and the acid solution of the diazo component described aboveis added thereto. The pH of the reaction solution is adjusted to 6.5 bycareful addition of 5% strength sodium hydroxide solution. The dyestuffof the formula ##SPC5##

has completely formed after 2 hours, and can be isolated by salting-out.(To avoid exceeding the critical pH value of 7, 0.5% strength sodiumhydroxide solution is used towards the end of the addition of the sodiumhydroxide).

The β-4-methoxy-1-naphthyl-ethyl alcohol used as intermediate productfor manufacturing the β-4-hydroxy-1-naphthyl-ethyl iodide can also beobtained as follows:

60 ml of solvent (preferably 1,2-dichloroethane or benzene) are treatedwith 17 g of powdered aluminium chloride in a 1--1 three-necked flaskfitted with stirrer, dropping funnel, and reflux cooler with calciumchloride tube, and 10 g of 1-methoxynaphthalene are added dropwise whilestirring and cooling with ice water. While stirring thoroughly, asolution consisting of 640 ml of solvent (preferably 1,2-dichloroethaneor benzene) and 5.4 g of ethylene oxide is subsequently added in such away that the internal temperature remains constant at approx. 20°C. Uponcompletion of the addition, the reaction mixture is poured on a mixtureof 1 kg of ice and 100 ml of concentrated hydrochloric acid. The organicphase is isolated, washed with water until neutral, dried over sodiumsulphate and the solvent is distilled off. The residual crude productcan be recrystallised from n-hexane/chloroform = 20/1. The resultingβ-4-methoxy-1-naphthyl-ethyl alcohol has a melting point of 86° - 87°C.

EXAMPLE 2

10 g of β-4 -hydroxy-1-naphthyl-ethyl iodide are dissolved in 250 ml ofether and introduced into a separating funnel. 250 ml of 2 N sodiumhydroxide solution are added thereto and the two phases are vigorouslyshaken for 15 minutes. The ether phase is now separated off and driedwith calcined sodium carbonate, and the ether is distilled off on arotary evaporator. The crude product which remains can be recrystallisedfrom ether/ligroin. The benzo[d]-spiro-[2,5]-octa-1,4-dien-3-oneobtained corresponds to the formula ##SPC6##

and shows a melting point of 97° - 98°C.

Dyeing Instruction for Cotton

20 g of woven cotton fabric are introduced into a solution whichcontains 0.6 g of dyestuff dissolved in 500 ml of water. The liquor isthen rendered alkaline with dilute sodium hydroxide solution, up to a pHvalue of at most 11.5. After 15 minutes, 50 g of sodium chloride areadded and dissolved whilst warming the liquor to 50°C. The dyeingsolution is kept for one hour at 50°C. The fabric is then squeezed outand dried for 5 minutes at 120°C. A fast dyeing results.

Equally good dyeing results can be achieved if the 5 minutes' drying isomitted.

By dyestuffs are to be understood in this context the4-(β-X-ethylnaphth-(1)-ols, for example of the formula ##SPC7##

and the corresponding spiro compounds, for example of the formula##SPC8##

Dyeing Instruction for Wool

A solution containing 0.6 g of a dyestuff of the general formula##SPC9##

in which X represents a chlorine, bromine or iodine atom or a quaternaryammonium group and R represents an aromatic radical, dissolved in 500 mlof water, is rendered alkaline (pH 12) with dilute sodium hydroxidesolution. After 90 minutes, the solution is acidified to pH 8 withglacial acetic acid. 20 Grams of wool fabric are then introduced intothis bath, which is adjusted to pH 4 to 5 by adding further glacialacetic acid. 50 Grams of sodium chloride are then added and the bathheated to 30°C. After 30 minutes, the fabric is squeezed out at 30°C anddried for 15 minutes at 60°C.

Equally good dyeing results can be attained if the 15 minutes drying isomitted.

If the corresponding spiro compound is used as dyestuff, the solution isnot rendered alkaline before the fabric is added.

EXAMPLE 3

10 Grams of β-4-hydroxy-1-naphthyl-ethyl chloride are dissolved in 300ml of chloroform and the solution is cooled to 0°C. Chlorosulphonic acidis dropwise added thereto, the temperature of the reaction mixture beingkept preferably at 0° to 5°C. Upon completion of the addition, thereaction mixture is heated to room temperature within 30 minutes, thenpoured on ice. The chloroform phase is isolated, dried with sodiumcarbonate and the chloroform distilled off. The residual crude productcan be recrystallised from n-hexane. The resulting product correspondsto the formula ##SPC10##

and has a melting point of 126° - 127°C.

The equimolar amount of the above described sulphochloride is introducedin small amounts into a solution of the compound of the formula##SPC11##

in pyridine, whilst stirring and at room temperature. Upon completion ofthe reaction, the pyridine is distilled off. The residual product isdissolved in water, then treated with an equal amount of ethyl alcoholand filtered. The reactive dyestuff is obtained by salting it out fromthe filtrate with sodium chloride.

EXAMPLE 4

The compound of the formula ##SPC12##

(instead of which the corresponding spiro compound can also be used) isdissolved in water and treated with 1 to 5 times the equimolar amount ofpotassium cyanide at 0° to 60°C. After 1 to 30 minutes the compound ofthe formula ##SPC13##

precipitates (optionally, only after concentrating) from the reactionmixture and can be filtered off.

In methanol as solvent, the compound of the formula ##SPC14##

having a decomposition point of 250° to 252°C, is likewise obtained fromthe compound of the formula ##SPC15##

If the two above described heterocyclic spiro compounds are diazotisedand coupled to the 2-hydroxy-naphthalene-3,6-disulphonic acid, reddyestuffs are obtained.

We claim:
 1. A compound of the formula ##SPC16##wherein X is chlorine,bromine or iodine.
 2. The compound of claim 1, wherein X is chlorine.